Sterilizing water-based ink and preparation method thereof

Abstract

The invention discloses degerming water-based ink and a preparation method thereof.The degerming water-based ink is prepared from, by weight, 30-50 parts of composite resin, 3-8 parts of antibacterial agent, 10-25 parts of pigment, 1-2 parts of dispersing agent, 0.1-0.5 part of defoaming agent, 1-2 parts of cross-linking agent, 0.5-2 parts of slow drying agent and 20-40 parts of solvent, and the composite resin is a composite system of water-based acrylic resin and water-based epoxy resin; the antibacterial agent comprises an inorganic antibacterial component, an organic antibacterial component and a synergist. The antibacterial printing ink has the advantages that excellent printing performance of the printing ink is maintained, and meanwhile, the antibacterial printing ink has a broad-spectrum, efficient and lasting antibacterial function.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of printing materials, in particular to a sterilization water-based ink and a preparation method thereof. BACKGROUND

[0002] Water-based ink has been widely used in food packaging, medicine packaging, daily necessities packaging and other fields because it uses water as the main solvent, has low VOC emission, is environmentally friendly and safe, etc. With the increasing demand of consumers for the hygiene and safety of packaging, packaging materials with sterilization function have become the development trend of the industry, and the sterilization performance of ink as the key functional layer of the packaging surface directly affects the storage shelf life and use safety of the products inside the packaging.

[0003] In the prior art, the sterilization modification of water-based ink for packaging mainly has the following defects: Poor sterilization effect and insufficient durability: Most inks only achieve preliminary sterilization by adding a single sterilization agent, and the sterilization rate of common pathogenic bacteria such as Escherichia coli and Staphylococcus aureus is less than 95%, and the sterilization efficiency decays by more than 10% after 3 months of storage, which cannot meet the long-term storage requirements; Poor compatibility of sterilization agents with ink systems: the interface compatibility of commonly used chlorine-containing sterilization agents and ordinary quaternary ammonium salt sterilization agents with water-based resins and pigments and fillers is poor, which leads to stability problems such as layering, precipitation and viscosity mutation of the ink, and reduces the printing adhesion and friction resistance; Safety hazards: some sterilization agents have toxic residues, excessive heavy metal and VOC content, which do not meet the requirements of relevant regulations such as GB 9685-2016 "Standard for the Use of Additives for Food Contact Materials and Products"; It is difficult to balance printing performance and sterilization performance: increasing the amount of sterilization agent to improve sterilization effect can easily lead to slow drying speed and poor leveling of the ink, affecting the industrial printing efficiency. SUMMARY

[0004] The purpose of the present application is to provide a sterilization water-based ink and a preparation method thereof, so that the ink has excellent printing performance and broad-spectrum, efficient and durable sterilization function.

[0005] The above technical purpose of the present application is achieved by the following technical solution: A sterilization water-based ink, comprising the following components by weight: 30-50 parts of a composite resin, 3-8 parts of an antibacterial agent, 10-25 parts of a pigment, 1-2 parts of a dispersing agent, 0.1-0.5 parts of an antifoaming agent, 1-2 parts of a crosslinking agent, 0.5-2 parts of a slow-drying agent and 20-40 parts of a solvent, the composite resin is a composite system of water-based acrylic resin and water-based epoxy resin, and the antibacterial agent comprises inorganic antibacterial components, organic antibacterial components and synergists.

[0006] Preferably, the mass ratio of the aqueous acrylic resin to the aqueous epoxy resin in the composite resin is 3-5:1, the aqueous acrylic resin is a core-shell structured acrylic emulsion with a glass transition temperature of-10-10℃, and the aqueous epoxy resin is an aqueous dispersion of bisphenol A type epoxy resin with an epoxy value of 0.15-0.25 eq / 100 g.

[0007] Preferably, the mass fraction of the inorganic antibacterial component in the antibacterial agent is 50%-70%, the mass fraction of the organic antibacterial component is 20-40%, and the mass fraction of the synergist is 5-15%. The inorganic antibacterial component includes zinc-doped titanium dioxide and silver-loaded diatomite at a mass ratio of 1:1. The organic antibacterial component includes guanidine polymer and natural plant extract at a mass ratio of 2:1. The guanidine polymer is polyhexamethylene biguanide hydrochloride with a molecular weight of 2000-3000. The natural plant extract includes Coptis deltoidea extract and cinnamaldehyde at a mass ratio of 1:1. The synergist is mesoporous silica modified by an aminosilane coupling agent, with a pore size of 5-15 nm and a specific surface area greater than 800 m² / g.

[0008] Preferably, the pigment is selected from one or more of rutile titanium dioxide, phthalocyanine blue, phthalocyanine green, permanent yellow, and carbon black, and the pigment particle size is 0.1-0.5 μm.

[0009] Preferably, the dispersant is selected from one of sodium polyacrylate or modified polyurethane dispersants.

[0010] Preferably, the defoaming agent is selected from one of mineral oil-based defoaming agents or silicone-based defoaming agents.

[0011] Preferably, the slow-drying agent is selected from one of ethylene glycol monobutyl ether or diethylene glycol monobutyl ether.

[0012] Preferably, the crosslinking agent is selected from one of aziridine-based crosslinking agents or carbodiimide-based crosslinking agents.

[0013] Preferably, the solvent is deionized water and ethanol at a weight ratio of 3-5:1.

[0014] A method for preparing a sterilized aqueous ink includes the following steps: Pre-dispersion: a portion of the solvent, the dispersant, and the defoaming agent are added to a batching tank, and low-speed stirring is performed to mix and homogenize; Pigment dispersion: the pigments and the composite antibacterial agent are added, and high-speed stirring is performed at 800-1200 rpm for 20-40 minutes to perform pre-dispersion; Grinding: the pre-dispersed slurry is transferred to a sand mill, zirconium oxide beads with a particle size of 0.4-0.6 mm are added, and grinding is performed for 2-4 hours until the fineness reaches ≤10 μm; Dispensing: the ground slurry is transferred to a mixing tank, composite resin, slow drying agent and crosslinking agent are added, and moderate stirring is carried out at 400-600 rpm for 40-60 minutes; Filtration: filtered through a 200-300 mesh screen to obtain the final product.

[0015] In summary, the present application has the following advantages: 1. The present application realizes the synergistic antibacterial effect of multiple mechanisms and multiple targets by compounding inorganic antibacterial components (zinc-doped titanium dioxide and silver-loaded diatomite) with organic antibacterial components (guanidine polymer and natural plant extract), solving the problem of narrow antibacterial spectrum of single antibacterial agent.

[0016] 2. The present application uses surface-functionalized mesoporous silica nanospheres and the porous structure of diatomite as carriers of antibacterial components, which not only improves the dispersibility and stability of the antibacterial components in the ink, but also realizes long-acting antibacterial effect through controlled release, reducing the migration of the antibacterial components.

[0017] 3. The present application significantly reduces the risk of heavy metal ion migration to the contents of the package by immobilizing and controlling the release of the antibacterial components, improving the safety of food and medical packaging; at the same time, using water as the main solvent conforms to the development direction of green chemistry.

[0018] 4. The multiple antibacterial components of the present application have good compatibility with the composite resin, are not prone to agglomeration and sedimentation, and at the same time have excellent adhesion, wear resistance, water resistance and chemical resistance, suitable for various packaging materials, in addition, the ink has suitable viscosity, drying speed and leveling property, suitable for various printing methods such as gravure printing and flexographic printing. DETAILED DESCRIPTION

[0019] The specific embodiments of the present application are further described below, and the embodiments do not constitute a limitation on the present application.

[0020] An antibacterial water-based ink comprises the following components by weight: 30-50 parts of composite resin, 3-8 parts of antibacterial agent, 10-25 parts of pigment, 1-2 parts of dispersing agent, 0.1-0.5 parts of defoaming agent, 1-2 parts of crosslinking agent, 0.5-2 parts of slow drying agent and 20-40 parts of solvent, the composite resin is a composite system of water-based acrylic resin and water-based epoxy resin, the antibacterial agent comprises inorganic antibacterial components, organic antibacterial components and synergists.

[0021] The mass ratio of water-based acrylic resin to water-based epoxy resin in the composite resin is 3-5:1, the water-based acrylic resin is a core-shell structure acrylic emulsion with a glass transition temperature of -10-10℃, and the water-based epoxy resin is a water-based dispersion of bisphenol A type epoxy resin with an epoxy value of 0.15-0.25 eq / 100g.

[0022] The inorganic antibacterial component in the antibacterial agent is 50-70% by mass, the organic antibacterial component is 20-40% by mass, and the synergist is 5-15% by mass. The inorganic antibacterial component includes zinc-doped titanium dioxide and silver-loaded diatomite at a mass ratio of 1:1. The organic antibacterial component includes guanidine polymer and natural plant extract at a mass ratio of 2:1. The guanidine polymer is polyhexamethylene biguanide hydrochloride with a molecular weight of 2000-3000. The natural plant extract includes extract of Coptis chinensis and cinnamaldehyde at a mass ratio of 1:1. The synergist is mesoporous silica modified by an aminosilane coupling agent, with a pore size of 5-15 nm and a specific surface area of greater than 800 m² / g.

[0023] The pigment is selected from one or more of rutile titanium dioxide, phthalocyanine blue, phthalocyanine green, permanent yellow, and carbon black, and the pigment particle size is 0.1-0.5 μm.

[0024] The dispersant is selected from one of sodium polyacrylate or modified polyurethane dispersants.

[0025] The defoaming agent is selected from one of mineral oil-based defoaming agents or silicone-based defoaming agents.

[0026] The slow-drying agent is selected from one of ethylene glycol monobutyl ether or diethylene glycol monobutyl ether.

[0027] The crosslinking agent is selected from one of aziridine crosslinking agents or carbodiimide crosslinking agents.

[0028] The solvent is deionized water and ethanol at a weight ratio of 3-5:1.

[0029] A method for preparing a bactericidal water-based ink includes the following steps: Pre-dispersion: a portion of the solvent, the dispersant, and the defoaming agent are added to a batching tank, and are mixed uniformly at low speed; Pigment dispersion: the pigments and the composite antibacterial agent are added, and are pre-dispersed at high speed at 800-1200 rpm for 20-40 minutes; Grinding: the pre-dispersed slurry is transferred to a sand mill, and zirconium oxide beads with a particle size of 0.4-0.6 mm are added, and are ground for 2-4 hours until the fineness reaches ≤10 μm; Formulation: the ground slurry is transferred to a mixing tank, and the composite resin, the slow-drying agent, and the crosslinking agent are added, and are mixed at medium speed at 400-600 rpm for 40-60 minutes; Filtration: the final product is obtained by filtration through a 200-300 mesh screen.

[0030] Example 1 A bactericidal water-based ink includes the following components by weight: 35 parts of a composite resin, 5 parts of an antibacterial agent, 12 parts of a pigment, 2 parts of a dispersing agent, 0.3 parts of an antifoaming agent, 2 parts of a crosslinking agent, 1 part of a slow-drying agent, and 30 parts of a solvent. The mass ratio of the water-based acrylic resin to the water-based epoxy resin in the composite resin is 4:1, the mass fraction of the inorganic antibacterial component in the antibacterial agent is 50%, the mass fraction of the organic antibacterial component is 40%, the mass fraction of the synergist is 10%, the pigment is phthalocyanine blue, the dispersing agent is a modified polyurethane dispersing agent, the antifoaming agent is a silicone antifoaming agent, the slow-drying agent is diethylene glycol monobutyl ether, the crosslinking agent is an aziridine crosslinking agent, and the solvent is deionized water and ethanol in a weight ratio of 4:1.

[0031] Example 2 A bactericidal water-based ink includes the following components by weight: 30 parts of a composite resin, 3 parts of an antibacterial agent, 10 parts of a pigment, 1 part of a dispersing agent, 0.1 parts of an antifoaming agent, 1 part of a crosslinking agent, 0.5 parts of a slow-drying agent, and 20 parts of a solvent. The mass ratio of the water-based acrylic resin to the water-based epoxy resin in the composite resin is 5:1, the mass fraction of the inorganic antibacterial component in the antibacterial agent is 55%, the mass fraction of the organic antibacterial component is 30%, the mass fraction of the synergist is 15%, the pigment is rutile titanium dioxide, the dispersing agent is a polyacrylic acid sodium salt dispersing agent, the antifoaming agent is a mineral oil-based antifoaming agent, the slow-drying agent is ethylene glycol monobutyl ether, the crosslinking agent is an aziridine crosslinking agent, and the solvent is deionized water and ethanol in a weight ratio of 5:1.

[0032] Example 3 A bactericidal water-based ink includes the following components by weight: 35 parts of a composite resin, 6 parts of an antibacterial agent, 17 parts of a pigment, 1 part of a dispersing agent, 0.5 parts of an antifoaming agent, 1 part of a crosslinking agent, 0.5 parts of a slow-drying agent, and 20 parts of a solvent. The mass ratio of the water-based acrylic resin to the water-based epoxy resin in the composite resin is 5:1, the mass fraction of the inorganic antibacterial component in the antibacterial agent is 70%, the mass fraction of the organic antibacterial component is 20%, the mass fraction of the synergist is 10%, the pigment is phthalocyanine green, the dispersing agent is a polyacrylic acid sodium salt, the antifoaming agent is a silicone antifoaming agent, the slow-drying agent is ethylene glycol monobutyl ether, the crosslinking agent is a carbodiimide crosslinking agent, and the solvent is deionized water and ethanol in a weight ratio of 3:1.

[0033] Example 4 A kind of bacteria-removing water-based ink, comprising the following components by weight parts: composite resin 50 parts, antibacterial agent 8 parts, pigment 25 parts, dispersing agent 2 parts, defoaming agent 0.5 parts, crosslinking agent 2 parts, slow drying agent 2 parts and solvent 40 parts.The mass ratio of water-based acrylic resin and water-based epoxy resin in composite resin is 5:1, the mass fraction of inorganic antibacterial component in antibacterial agent is 70%, the mass fraction of organic antibacterial component is 25%, the mass fraction of synergist is 5%, the pigment is permanent yellow, the dispersing agent is modified polyurethane dispersing agent, the defoaming agent is mineral oil-based defoaming agent, the slow drying agent is diethylene glycol monobutyl ether, the crosslinking agent is aziridine crosslinking agent, and the solvent is deionized water and ethanol with weight ratio of 5:1.

[0034] According to GB / T 21866-2008 "Antibacterial Performance Test Method of Antibacterial Coatings" and ISO 22196:2011 "Evaluation Method of Antibacterial Performance of Plastic Products Surface", the antibacterial performance of the bacteria-removing water-based ink prepared in the above examples and the commercially available ordinary water-based ink is tested, and the basic physical performance of the ink is tested, and the results are shown in Table 1: Table 1

[0035] As can be seen from Table 1, the bacteria-removing water-based ink prepared by the present application shows extremely high antibacterial rate on various test bacteria compared with ordinary water-based ink, and has wide antibacterial spectrum and good effect on bacteria and fungi. At the same time, the fineness, viscosity and other printing suitability are equivalent to ordinary water-based ink, and the adhesion, wear resistance and water resistance are excellent.

[0036] The above is only a preferred embodiment of the present application and is not intended to limit the present application. Those skilled in the art can make various modifications or equivalent replacements to the present application within the spirit and protection scope of the present application, and such modifications or equivalent replacements should also be considered to fall within the protection scope of the technical solutions of the present application.

Claims

1. A bactericidal water-based ink, characterized in that, The product comprises the following components by weight: 30-50 parts of composite resin, 3-8 parts of antibacterial agent, 10-25 parts of pigment, 1-2 parts of dispersant, 0.1-0.5 parts of defoamer, 1-2 parts of crosslinking agent, 0.5-2 parts of slow-drying agent, and 20-40 parts of solvent. The composite resin is a composite system of waterborne acrylic resin and waterborne epoxy resin. The antibacterial agent includes inorganic antibacterial components, organic antibacterial components, and synergists.

2. The antibacterial water-based ink according to claim 1, characterized in that: The mass ratio of waterborne acrylic resin to waterborne epoxy resin in the composite resin is 3~5:

1. The waterborne acrylic resin is a core-shell structured acrylic emulsion with a glass transition temperature of -10~10℃. The waterborne epoxy resin is an waterborne dispersion of bisphenol A type epoxy resin with an epoxy value of 0.15~0.25 eq / 100g.

3. The antibacterial water-based ink according to claim 1, characterized in that: The antibacterial agent comprises 50%–70% inorganic antibacterial components, 20%–40% organic antibacterial components, and 5%–15% synergist. The inorganic antibacterial components include zinc-doped titanium dioxide and silver-supported diatomaceous earth in a 1:1 mass ratio. The organic antibacterial components include guanidine polymers and natural plant extracts in a 2:1 mass ratio. The guanidine polymer is polyhexamethylene biguanide hydrochloride with a molecular weight of 2000–3000. The natural plant extracts include Coptis chinensis extract and cinnamaldehyde in a 1:1 mass ratio. The synergist is mesoporous silica modified with an aminosilane coupling agent, with a pore size of 5–15 nm and a specific surface area greater than 800 m² / g.

4. The antibacterial water-based ink according to claim 1, characterized in that: The pigment is selected from one or more of rutile titanium dioxide, phthalocyanine blue, phthalocyanine green, permanent yellow, and carbon black, and the pigment particle size is 0.1~0.5μm.

5. The antibacterial water-based ink according to claim 1, characterized in that: The dispersant is selected from sodium polyacrylate or modified polyurethane dispersants.

6. The antibacterial water-based ink according to claim 1, characterized in that: The defoamer is selected from mineral oil-based defoamers or organosilicon-based defoamers.

7. The antibacterial water-based ink according to claim 1, characterized in that: The slow-drying agent is selected from either ethylene glycol monobutyl ether or diethylene glycol monobutyl ether.

8. The antibacterial water-based ink according to claim 1, characterized in that: The crosslinking agent is selected from either aziridine crosslinking agents or carbodiimide crosslinking agents.

9. The antibacterial water-based ink according to claim 1, characterized in that: The solvent is deionized water and ethanol in a weight ratio of 3 to 5:

1.

10. A method for preparing an antibacterial water-based ink according to any one of claims 1 to 9, characterized in that: Includes the following steps: Pre-dispersion: Add a portion of the solvent, dispersant, and defoamer by weight to the mixing tank and mix thoroughly by low-speed stirring; Pigment dispersion: Add pigment and compound antibacterial agent, stir at high speed of 800~1200 rpm for 20~40 minutes to pre-disperde; Grinding: Transfer the pre-dispersed slurry to a sand mill, add zirconia beads with a particle size of 0.4~0.6mm, and grind for 2~4 hours until the fineness reaches ≤10μm; Preparation: Transfer the ground slurry to a mixing tank, add the composite resin, slow drying agent and crosslinking agent, and stir at medium speed of 400~600 rpm for 40~60 minutes; Filtration: The final product is obtained by filtering through a 200-300 mesh sieve.

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